JPS6393746A - Production of carboxylic acid - Google Patents
Production of carboxylic acidInfo
- Publication number
- JPS6393746A JPS6393746A JP61240129A JP24012986A JPS6393746A JP S6393746 A JPS6393746 A JP S6393746A JP 61240129 A JP61240129 A JP 61240129A JP 24012986 A JP24012986 A JP 24012986A JP S6393746 A JPS6393746 A JP S6393746A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- hydrogen peroxide
- olefins
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 23
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 20
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 11
- 238000007248 oxidative elimination reaction Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 238000000034 method Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 10
- 239000011964 heteropoly acid Substances 0.000 abstract description 10
- 125000005842 heteroatom Chemical group 0.000 abstract description 5
- 150000007513 acids Chemical class 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 2
- 150000003949 imides Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 238000010813 internal standard method Methods 0.000 description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- -1 chromium yaruthenium Chemical class 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical class [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、オレフィン類を酸化開裂することによるカル
ボン酸の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing carboxylic acids by oxidative cleavage of olefins.
[従来の技術]
石油や動植物油脂から大量かつ安価に得られるオレフィ
ン類の不飽和結合を酸化開裂して得られるカルホン酸は
、エステル、イミド、アミド等の)京料として広範囲に
利用されている。[Prior art] Carphonic acids obtained by oxidative cleavage of unsaturated bonds in olefins, which are obtained in large quantities and at low cost from petroleum, animal and vegetable oils, are widely used as synthetic materials (such as esters, imides, amides, etc.). .
オレフィン類を酸化開裂してカルボン酸を製造する方法
については、これまでにも種々提案されている。例えば
、過マンガン酸カリウム、重クロム酸カリウム、四酸化
ルテニウム等の金属化合物により酸化する方法や、これ
らのものを触媒量加え、次亜塩素酸ナトリウムや過ヨウ
素酸ナトリウム等の酸化剤を用いる方法(Bull、C
henv、Soc、Jpn。Various methods have been proposed to date for producing carboxylic acids by oxidative cleavage of olefins. For example, a method of oxidizing with a metal compound such as potassium permanganate, potassium dichromate, or ruthenium tetroxide, or a method of adding a catalytic amount of these compounds and using an oxidizing agent such as sodium hypochlorite or sodium periodate. (Bull, C.
henv, Soc, Jpn.
、 59.2637(1986))等が知られている。, 59.2637 (1986)), etc. are known.
し発明が解決しようとする問題点コ
しかしながら、これらの方法はクロムヤルテニウムのよ
うに金属に毒性があったり、又、次亜塩素酸ナトリウム
や過ヨウ素酸ナトリウム等にあっては腐蝕性があるうえ
に高価であることから実用に耐えないもので必っだ。更
にこれらの酸化剤は、酸性条件下では不安定で、反応は
塩基性の条件下で行なわなければならない。このため中
和工程を必要とし、製造工程が煩雑となり工業的には不
利である。これらのことからオレフィン類を酸性条件下
で酸化開裂させ、安全かつ安価にカルボン酸を製造する
方法が望まれていた。Problems that the invention seeks to solve:However, these methods are not suitable for metals such as chromium yaruthenium, which are toxic, and sodium hypochlorite and sodium periodate, which are corrosive. Furthermore, it is expensive and therefore impractical. Furthermore, these oxidizing agents are unstable under acidic conditions and the reaction must be carried out under basic conditions. Therefore, a neutralization step is required, making the manufacturing process complicated and industrially disadvantageous. For these reasons, a method for producing carboxylic acids safely and inexpensively by oxidatively cleaving olefins under acidic conditions has been desired.
過酸化水素は、安価で腐蝕性がなく、酸性下で安定であ
ることからカルボン酸の製造における適切な酸化剤であ
る。しかし、このものは水溶性であるため、油溶性物質
に作用させる場合にはタングステン酸やモリブデン酸に
アルキル置換アンモニウムやホスホニウム等を導入して
油溶性を付与したごとき特殊で高価な触媒を使用する方
法(特開昭60−34921>が知られているのみであ
って、水溶性の触媒を適用する方法については未だ知ら
れていない。Hydrogen peroxide is a suitable oxidizing agent in the production of carboxylic acids because it is inexpensive, noncorrosive, and stable under acidic conditions. However, since this substance is water-soluble, when it acts on oil-soluble substances, special and expensive catalysts such as those made by introducing alkyl-substituted ammonium or phosphonium into tungstic acid or molybdic acid to make it oil-soluble are used. Only a method (JP-A-60-34921) is known, and a method using a water-soluble catalyst is not yet known.
又、上記の方法の如くナトリウム、カリウム、アンモニ
ウム、ホスホニウム等のカチオンが反応系に共存する場
合には生成するカルボン酸の純度や収率が低下し、更に
別途精製工程を必要とする等実用上問題がおる。即ち、
カルボン酸を簡便かつ安価に製造するためにはプロトン
以外のいかなるカチオンの存在も製造上不利益を生ずる
。In addition, when cations such as sodium, potassium, ammonium, phosphonium, etc. coexist in the reaction system as in the above method, the purity and yield of the produced carboxylic acid decreases, and a separate purification process is required. There's a problem. That is,
In order to easily and inexpensively produce carboxylic acids, the presence of any cation other than protons causes disadvantages in production.
ところが本発明者らの研究によれば予想外のことに油溶
性のないタングステン酸であっても何ら上記のごとき処
理を施すことなく触媒として使用し、過酸化水素を酸化
剤としてオレフィン類に作用させることにより極めて効
果的に二重結合が酸化開裂され、対応するモノ及σ/又
はジカルボン酸が得られることが明らかとなった。又、
上記タングステン酸と同様にモリブデン酸を触媒として
用いた場合にもオレフィン類の二重結合が酸化開裂され
ることが見い出された。However, according to research conducted by the present inventors, it was unexpectedly possible to use tungstic acid, which is not oil-soluble, as a catalyst without any of the above treatments, and to use hydrogen peroxide as an oxidizing agent to act on olefins. It has been revealed that by doing so, the double bond is oxidatively cleaved very effectively and the corresponding mono- and σ/or dicarboxylic acids are obtained. or,
It has been found that the double bonds of olefins are oxidatively cleaved when molybdic acid is used as a catalyst, similar to the above-mentioned tungstic acid.
更に本発明者らは、タングステン酸又はモリブデン酸の
へテロポリ酸を触媒として用いる場合にも、オレフィン
類の二重結合が過酸化水素により効率よく酸化開裂され
、対応するモノ及び/又はジカルボン酸が高収率、高純
度で製造できることを見い出した。Furthermore, the present inventors have found that when using a heteropolyacid such as tungstic acid or molybdic acid as a catalyst, the double bonds of olefins are efficiently oxidized and cleaved by hydrogen peroxide, and the corresponding mono- and/or dicarboxylic acid is It has been found that it can be produced with high yield and high purity.
本発明は、上記の新知見に基づいて完成されたものであ
る。The present invention was completed based on the above new findings.
即ち、本発明は、オレフィン類を過酸化水素により酸化
開裂してカルボン酸を製造する方法に当っての新規有用
な触媒を提供することを目的とする。That is, an object of the present invention is to provide a novel and useful catalyst for a method of producing carboxylic acid by oxidative cleavage of olefins with hydrogen peroxide.
[問題点を解決するための手段]
本発明は、オレフィン類を酸化開裂してカルボン酸を製
造するに当り、タングステン酸、モリブデン酸及びそれ
らのへテロポリ酸からなる群から選ばれる1種又は2種
以上の触媒の存在下、過酸化水素により酸化開裂するこ
とを発明の要旨とする。[Means for Solving the Problems] The present invention provides for the production of carboxylic acids by oxidative cleavage of olefins using one or two selected from the group consisting of tungstic acid, molybdic acid, and their heteropolyacids. The gist of the invention is to perform oxidative cleavage with hydrogen peroxide in the presence of more than one type of catalyst.
本発明におけるオレフィン類としては、ブテン、ペンテ
ン、ヘキセン、オクテン、シクロペンテン、シクロヘキ
セン、シクロオクテン等の炭素数4〜8の脂肪族、脂環
族炭化水素、ジシクロベンテノール、スルホレン、ホロ
ン、イソホロン、オレイン酸、パルミトレイン酸、リノ
ール酸、リルイン酸、ワシルイン酸及びそれらのエステ
ル等のカルボニル基、水酸基、カルボキシル基、エステ
ル基、スルホン暴等の官能基を有するオレフィンが例示
される。上記官能基は、本発明に係る反応を阻害するも
のでなければ、オレフィン類と同様に酸化される基であ
ってもよく、条件によっては反応の進行に寄与する場合
がある。Olefins in the present invention include aliphatic and alicyclic hydrocarbons having 4 to 8 carbon atoms such as butene, pentene, hexene, octene, cyclopentene, cyclohexene, cyclooctene, dicyclobentenol, sulfolene, holone, isophorone, Examples include olefins having functional groups such as carbonyl groups, hydroxyl groups, carboxyl groups, ester groups, and sulfonyl groups, such as oleic acid, palmitoleic acid, linoleic acid, lyluic acid, wasylic acid, and esters thereof. The above-mentioned functional group may be a group that is oxidized like olefins, as long as it does not inhibit the reaction according to the present invention, and may contribute to the progress of the reaction depending on the conditions.
本発明に係る触媒としては、タングステン酸、モリブデ
ン酸、あるいはこれらのへテロポリ酸が掲げられる。こ
こにいうヘテロポリ酸とは、2種以上の酸素酸からなる
縮合酸であり、ポリ酸原子としては、タングステン及び
モリブデンであり、ヘテロ原子としては、以下に示すよ
うな各種のものが使用できる。タングステン酸のへテロ
ポリ酸におけるヘテロ原子としCは、P、AS、Si。Examples of the catalyst according to the present invention include tungstic acid, molybdic acid, and heteropolyacids thereof. The heteropolyacid referred to herein is a condensed acid consisting of two or more types of oxyacids, and the polyacid atoms include tungsten and molybdenum, and the heteroatoms include the following various types. The heteroatom C in the heteropolyacid of tungstic acid is P, AS, or Si.
Ti、Co、Fe、B、V、Be、l N i、Ga等
が例示される。タングステン酸のへテロポリ酸の具体例
しては、次の構造式、
H3(PW1204o)、
H3(ASW12040)、
H4(S ! W18O49)、
H4(T ! W18O49)、
H5(COW12040)、
H5(FeW12040)、
H5〔BW1204o〕、
H3〔VW1204o〕、
H6(B eWg 031)、
H6(TeW6024)、
H5〔IW6024〕、
H4(N ! W602486 )、
H3(GaW6 o24”6 )、
H6(P2W18062〕・
H(AS2W13062)、
H7〔PW11033〕
を有するものが例示できる。Examples include Ti, Co, Fe, B, V, Be, lNi, Ga, and the like. Specific examples of heteropolyacids of tungstic acid are as follows: ), H5 [BW1204o], H3 [VW1204o], H6 (BeWg 031), H6 (TeW6024), H5 [IW6024], H4 (N! W602486), H3 (GaW6 o24”6), H6 (P2 W18062]・H (AS2W13062) and H7[PW11033].
又、モリブデン酸のへテロポリ酸におけるヘテロ原子と
しては、P、AS、Si、Ge、Ti、Ce、Th、M
n5N i、Te、L Co5Cr、Fe5Ga等が例
示される。モリブデン酸のへテロポリ酸の具体例として
は、次の構造式、H3(P M O12040)、
H3(ASMO12040)・
H4(S I M O12040)、
町(G e M O12040)、
H4(T ! M O12040)、
HB (08MO12042)、
HB (ThMO12042)・
H7(PM01103.)、
H7(ASM01103g)、
HB (G e M 01103g)、H6(MnMO
9032)、
H6(N ! M O9032)、
H6(TeMOs024)、
H5(IMo6024)、
H3(COM Os 024H6)、
H3(Cr M O6024H6)、
H3(F eMOs o24”6 )、H3(GaMO
6024H6)、
H4(N t Mo6 o24”B )、H6(P 2
M O13062)、
H6(AS2 MOH3062)
を有するもの等が例示できる。In addition, the heteroatoms in the heteropolyacid of molybdic acid include P, AS, Si, Ge, Ti, Ce, Th, M
Examples include n5N i, Te, L Co5Cr, and Fe5Ga. Specific examples of heteropolyacids of molybdic acid include the following structural formulas: H3 (P M O12040), H3 (ASMO12040), H4 (SI M O12040), Machi (G e M O12040), H4 (T! M O12040), HB (08MO12042), HB (ThMO12042), H7 (PM01103.), H7 (ASM01103g), HB (G e M 01103g), H6 (MnMO
9032), H6 (N! M O9032), H6 (TeMOs024), H5 (IMo6024), H3 (COM Os 024H6), H3 (Cr M O6024H6), H3 (FeMOs o24”6), H3 (GaMO
6024H6), H4(N t Mo6 o24”B ), H6(P 2
Examples include those having M013062) and H6 (AS2 MOH3062).
更に、各々の原子を2種以上配位させた混合配位ヘテロ
ポリ酸、例えば、
H4P M OW 11040゜
H4PReW1104o1
H4P VM O11040゜
H5P V 2 M O100401
H3PMO6W6040
等も使用可能である。上記に例示したこれらへテロポリ
酸はいずれも公知のものである。合成の容易さ又は入手
の容易さの観点からは、ヘテロ原子としてP又はSiを
含有するヘテロポリ酸が好ましく、特に
12−タングストリン酸(H3PW1204o)、12
−タングストケイM (H3S i W18O49)、
12−モリブドリン酸(H3PMO12040)等がよ
り好ましい。Furthermore, mixed coordination heteropolyacids in which two or more of each type of atoms are coordinated, such as H4P M OW 11040°H4PReW1104o1 H4P VM O11040°H5P V 2 M O100401 H3PMO6W6040, can also be used. All of these heteropolyacids exemplified above are known. From the viewpoint of ease of synthesis or availability, heteropolyacids containing P or Si as a heteroatom are preferred, particularly 12-tungstophosphoric acid (H3PW1204o), 12-tungstophosphoric acid (H3PW1204o),
-TungstoKi M (H3S i W18O49),
12-molybdophosphoric acid (H3PMO12040) and the like are more preferred.
又、上記触媒として用いるタングステン酸、モリブデン
酸又はこれらのへテロポリ酸は、水和物であってもよく
、更に、反応系内で上記のタングステン酸、モリブデン
酸又はこれらのへテロポリ酸を生成し1qる化合物の形
態であってもよい。このような化合物としては、MC3
、MC16及びMS3 (M=W又はMO)で表わされ
る酸化物、塩化物及び硫化物の形態が例示される。Further, the tungstic acid, molybdic acid, or a heteropolyacid thereof used as the catalyst may be a hydrate, and furthermore, the tungstic acid, molybdic acid, or a heteropolyacid thereof may be produced in the reaction system. It may be in the form of a 1q compound. Such compounds include MC3
, MC16 and MS3 (M=W or MO), oxides, chlorides and sulfides are exemplified.
このような酸化物、塩化物、硫化物を使用する場合には
、例えばリン酸、塩酸、硫酸等の鉱酸を反応系内に加え
、DH4以下の酸性条件下で反応を行なうことが好まし
い。又、触媒を酸の形態で加え、鉱酸を更に用いてもよ
い。When such oxides, chlorides, and sulfides are used, it is preferable to add a mineral acid such as phosphoric acid, hydrochloric acid, or sulfuric acid to the reaction system and conduct the reaction under acidic conditions of DH4 or less. Also, the catalyst may be added in acid form and mineral acids may also be used.
上記に例示した触媒は、単独で使用しても2種以上を併
用してもよい。The catalysts exemplified above may be used alone or in combination of two or more.
反応性からはへテロポリ酸が好ましく、反応性と価格と
のバランス上からはタングステン酸が好ましい。In terms of reactivity, heteropolyacids are preferred, and in terms of balance between reactivity and cost, tungstic acid is preferred.
本発明に係る製造法は、一般に次の如くして行なわれる
。即ち、反応器に原料であるオレフィン類及び触媒を仕
込み、過酸化水素を添加し、溶媒中で加熱撹拌下に反応
を行なう。The manufacturing method according to the present invention is generally carried out as follows. That is, olefins and a catalyst as raw materials are charged into a reactor, hydrogen peroxide is added, and the reaction is carried out in a solvent while being heated and stirred.
反応時のオレフィン類の濃度は、特に限定がない。しか
し、反応終了後、反応混合物を冷却し生成カルボン酸を
結晶化させて単離する場合には、結晶の析出量及び品質
等の観点から、オレフィン類の濃度は2〜70重量%程
度とするのが好ましく、15〜60重量%とするのがよ
り好ましい。The concentration of olefins during the reaction is not particularly limited. However, when the reaction mixture is cooled after the reaction is completed and the resulting carboxylic acid is crystallized and isolated, the concentration of olefins should be approximately 2 to 70% by weight from the viewpoint of the amount and quality of crystals precipitated. The content is preferably 15 to 60% by weight, and more preferably 15 to 60% by weight.
触媒の使用量は、触媒活性が発揮されるのに有効な量で
ある限り、広い範囲から選択される。しかし、反応速度
及び触媒のコストの観点からは、遊離酸(タングステン
酸、モリブデン酸又はこれらのへテロポリ酸)換算で、
オレフィン類に対し0.01〜30重量%程度、好まし
くは1〜10重量%程度が有利である。The amount of catalyst to be used is selected from a wide range as long as it is an effective amount to exhibit catalytic activity. However, from the viewpoint of reaction rate and catalyst cost, in terms of free acid (tungstic acid, molybdic acid, or their heteropolyacids),
Advantageously, the amount is about 0.01 to 30% by weight, preferably about 1 to 10% by weight, based on the olefins.
本反応に必要な過酸化水素の化学量論量はオレフィン類
1モルに対し4モルであるが、実際にはその10〜50
%過剰に使用するのが望ましい。The stoichiometric amount of hydrogen peroxide required for this reaction is 4 mol per 1 mol of olefins, but in reality it is 10 to 50 mol.
It is desirable to use % excess.
反応混合物中の過酸化水素の濃度は、広い範囲から選択
できる。その下限は、オレフィン類を酸化した触媒が過
酸化水素により酸化能力を回復するのに充分な濃度であ
って、かなり稀薄なものでも反応速度の低下は避けられ
ないものの酸化反応は進行する。又、上限は特に存在せ
ず、かなりの高濃度であってもよい。しかしながら、反
応速度を向上させ、かつ低濃度の過酸化水素を用いて製
造コストの低減を図る観点からは、0.1ミリモル/l
〜12モル/l程度、好ましくは10ミリモル/l〜8
モル/l程度が有利である。過酸化水素は、通常、水溶
液の形態で供給される。The concentration of hydrogen peroxide in the reaction mixture can be selected from a wide range. The lower limit is a concentration sufficient for the catalyst that has oxidized olefins to recover its oxidizing ability with hydrogen peroxide, and even if the catalyst is quite dilute, the oxidation reaction will proceed, although the reaction rate will inevitably decrease. Further, there is no particular upper limit, and the concentration may be quite high. However, from the viewpoint of improving the reaction rate and reducing production costs by using low concentration hydrogen peroxide, 0.1 mmol/l
- About 12 mol/l, preferably 10 mmol/l - 8
A value of the order of mol/l is advantageous. Hydrogen peroxide is usually supplied in the form of an aqueous solution.
反応溶媒としては、水が適当である。水と混和可能な有
機溶媒、例えば炭素数1〜4のアルコール、炭素数1〜
4のカルボン酸、ジオキサン、テトラヒドロフラン、ジ
メチルホルムアミド等を単独で使用し、又は均一相を保
つ範囲で水と併用することも可能である。Water is suitable as a reaction solvent. Water-miscible organic solvents, such as alcohols having 1 to 4 carbon atoms, and alcohols having 1 to 4 carbon atoms.
It is also possible to use the carboxylic acid No. 4, dioxane, tetrahydrofuran, dimethylformamide, etc. alone, or in combination with water within a range that maintains a homogeneous phase.
反応温度は、反応速度の点から、通常、20〜100℃
程度の温度範囲が採用されるが、加圧下で反応した場合
には150℃程度までの反応温度を採用することもでき
る。反応速度の観点及び過酸化水素の分解を防止又は抑
制する観点からは、50〜130℃程度にて反応を行な
うのが好ましい。The reaction temperature is usually 20 to 100°C from the viewpoint of reaction rate.
However, when the reaction is carried out under pressure, a reaction temperature of up to about 150° C. can also be employed. From the viewpoint of reaction rate and prevention or suppression of decomposition of hydrogen peroxide, it is preferable to carry out the reaction at about 50 to 130°C.
反応時間は、オレフィン類、触媒及び過酸化水素の濃度
、反応温度等により変わり得るが、通常1〜24時間程
度でおる。The reaction time may vary depending on the concentration of olefins, catalyst and hydrogen peroxide, reaction temperature, etc., but is usually about 1 to 24 hours.
反応終了後、生成したカルボン酸は、各々の物性により
適した方法で反応混合物から分離できる。After the reaction is completed, the produced carboxylic acid can be separated from the reaction mixture by a method more suitable for each physical property.
例えば、蒸留しても良いし、反応溶媒をトッピングした
後、任意の溶媒を用いて再結晶しても良い。For example, it may be distilled, or it may be topped with a reaction solvent and then recrystallized using any solvent.
反応混合物を徐冷してカルボン酸を結晶化させる方法に
おいて、触媒としてヘテロポリ酸、殊にタングステン酸
のへテロポリ酸を用いると、これらが水その他の反応溶
媒によく溶解するため清澄な反応混合物が得られ、当該
反応混合物を徐冷すると、生成カルボン酸は結晶として
析出し、上記触媒や未反応オレフィン類を溶解した母液
から濾過により極めて容易に分離できる。分離俊、母液
は再び反応に供することができ、触媒の失活も認められ
ない。単離された結晶は、そのまま乾燥するか、必要に
応じて水等で洗浄、再結晶して精製する。一方、触媒と
してタングステン酸又はモリブデン酸を用いる場合、反
応系内の過酸化水素濃度が低下すると、触媒が析出する
傾向があり、析出した触媒は生成カルボン酸と混入して
目的物の純度の低下を招く。よって、触媒としてタング
ステン酸又はモリブデン酸を用いる場合には、反応終了
後の単離工程においても過酸化水素濃度をこれら触媒が
溶解状態を保つ濃度以上に保持するか、あるいは反応直
後に、析出した触媒を濾過等によ分離しておいてから結
晶化を行なうのが望ましい。In the method of slowly cooling a reaction mixture to crystallize a carboxylic acid, when a heteropolyacid, especially a heteropolyacid such as tungstic acid, is used as a catalyst, a clear reaction mixture can be obtained because these heteropolyacids dissolve well in water and other reaction solvents. When the reaction mixture is slowly cooled, the produced carboxylic acid precipitates as crystals, and can be very easily separated by filtration from the mother liquor in which the catalyst and unreacted olefins are dissolved. After separation, the mother liquor can be used for the reaction again, and no deactivation of the catalyst is observed. The isolated crystals are purified by drying as they are, or by washing with water and recrystallizing if necessary. On the other hand, when using tungstic acid or molybdic acid as a catalyst, the catalyst tends to precipitate when the hydrogen peroxide concentration in the reaction system decreases, and the precipitated catalyst mixes with the produced carboxylic acid, reducing the purity of the target product. invite. Therefore, when using tungstic acid or molybdic acid as a catalyst, it is necessary to maintain the hydrogen peroxide concentration at a level above which these catalysts remain in a dissolved state even in the isolation step after the completion of the reaction, or to remove the precipitated hydrogen peroxide immediately after the reaction. It is desirable to perform crystallization after separating the catalyst by filtration or the like.
このような操作を行なうことにより、ヘテロポリ酸を用
いる場合と同等の高純度、高収率で目的カルボン酸を単
離することができる。By performing such an operation, the target carboxylic acid can be isolated with high purity and high yield equivalent to when using a heteropolyacid.
[実施例] 以下に実施例を掲げ、本発明の詳細な説明する。[Example] The present invention will be described in detail below with reference to Examples.
実施例1
撹拌機付ガラス製4つロフラスコにシクロヘキセン16
.89 (0,2モル)、60%過酸化水素水50Ij
(0,88モル)、タングステン酸0゜749を入れ、
激しく撹拌しながら、加熱還流させた。還流温度は74
°Cより100℃まで時間と共に上昇した。3時間反応
後、反応溶液のガスクロマトグラフィー内部標準法によ
り対応するカルボン酸の生成率を算出したところ、アジ
ピン酸95モル%、グルタル酸3モル%であった。この
反応溶液を冷却し、結晶化してアジピン酸の結晶を24
.59 (収率86モル%)得た。Example 1 Cyclohexene 16 in a glass 4-bottle flask with a stirrer
.. 89 (0.2 mol), 60% hydrogen peroxide solution 50 Ij
(0.88 mol), tungstic acid 0°749 was added,
The mixture was heated to reflux while stirring vigorously. Reflux temperature is 74
The temperature increased from °C to 100 °C over time. After 3 hours of reaction, the production rate of the corresponding carboxylic acid was calculated by gas chromatography internal standard method of the reaction solution, and was found to be 95 mol % of adipic acid and 3 mol % of glutaric acid. This reaction solution was cooled and crystallized to form adipic acid crystals at 24
.. 59 (yield 86 mol%) was obtained.
実施例2
ガラス製オートクレーブにシクロペンテン13゜69
(0,2モル)と60%過酸化水素水509.12−タ
ングストリン酸29水和物0.6gを仕ところ、カルボ
ン酸の生成率は、グルタル酸90モル%、コハク酸2モ
ル%でめった。この反応溶液の水をトッピングし、ベン
ゼンにより再結品して、グルタル酸の結晶22.69
(収率88モル%)を得た。Example 2 Cyclopentene 13°69 in a glass autoclave
(0.2 mol) and 60% hydrogen peroxide solution 509.12-tungstophosphoric acid 29 hydrate 0.6 g were used, and the production rate of carboxylic acid was 90 mol% of glutaric acid and 2 mol% of succinic acid. Rarely. This reaction solution was topped with water and re-crystallized with benzene to form crystals of glutaric acid.
(yield: 88 mol%).
実施例3
実施例1の反応器にシクロヘキセン16.89、ter
t−ブタノール303、モリブデン酸5.0gを仕込み
、加熱還流させながら、60%過酸化水素水50gを5
時間で滴下した。その後3時間速流して反応を終了した
。反応溶液をガスクロマトグラフィー内部標準法により
測定したところ、対応するカルボン酸の生成率は、アジ
ピン186モル%、グルタル酸2モル%であった。Example 3 Cyclohexene 16.89, ter
Charge 303 g of t-butanol and 5.0 g of molybdic acid, and while heating and refluxing, add 50 g of 60% hydrogen peroxide solution.
It dripped in time. Thereafter, the reaction was completed by rapid flow for 3 hours. When the reaction solution was measured by gas chromatography internal standard method, the production rate of the corresponding carboxylic acid was 186 mol % of adipine and 2 mol % of glutaric acid.
実施例4
触媒に12−モリブドリンw129水和物を3゜03を
用いる以外は実施例1と同様に反応を行なった。ガスク
ロマトグラフィー内部標準法により測定した結果、対応
するカルボン酸の生成率は、アジピン酸92モル%、グ
ルタル酸5モル%であった。Example 4 A reaction was carried out in the same manner as in Example 1, except that 3°03 of 12-molybdoline w129 hydrate was used as a catalyst. As a result of measurement by gas chromatography internal standard method, the production rate of the corresponding carboxylic acids was 92 mol% for adipic acid and 5 mol% for glutaric acid.
実施例5
実施例1の反応器にイソホロン27.6g(0゜2モル
)、水309.12−ダンゲストケイ酸24水和物1.
09を入れ、80℃で撹拌しながら、30%過酸化水素
水1409を3時間で滴下したところ、激しい発泡が見
られた。この発泡が停止するまで、8時間反応を続行し
た。反応溶液をガスクロマトグラフィー内部標準法によ
り測定したところ、3,3−ジメチルグルタル酸の生成
率は50モル%であった。イソホロンは検出できなかっ
た。Example 5 In the reactor of Example 1, 27.6 g (0.2 mol) of isophorone, 309.1 of water and 1.2-dungest silicic acid ditetrahydrate were added.
When 30% hydrogen peroxide solution 1409 was added dropwise over 3 hours while stirring at 80° C., intense foaming was observed. The reaction was continued for 8 hours until the bubbling stopped. When the reaction solution was measured by gas chromatography internal standard method, the production rate of 3,3-dimethylglutaric acid was 50 mol%. Isophorone could not be detected.
実施例6
実施例1の反応器にジシクロベンテノール30g(0,
2モル)、水609.12−タングストリン酸29水和
物0.9gを仕込ミ、90℃で撹拌しながら60%過酸
化水素水509を2時間で滴下し、更に4時間反応を行
なった。この反応溶液をガスクロマトグラフィー内部標
準法により測定した結果、対応するカルボン酸の生成率
は58モル%でめったが、この溶液の中和価を測定した
ところ、反応により0.44モルのカルボキシル基が生
成していた。そこで、更に60%過酸化水素水509と
触媒0.9gを加えて10時間反応を継続したところ、
トリカルボキシルシクロペンチル酢酸が60モル%の生
成率で得られたくガスクロマトグラフィー内部標準法に
よる)。この時、中和価から算出されるカルボキシル基
の生成量は0.73モル%であった。Example 6 Into the reactor of Example 1, 30 g of dicyclobentenol (0,
After charging 0.9 g of water 609.12-tungstophosphoric acid 29 hydrate (2 mol), 60% hydrogen peroxide solution 509 was added dropwise over 2 hours while stirring at 90°C, and the reaction was further carried out for 4 hours. . As a result of measuring this reaction solution by gas chromatography internal standard method, the production rate of the corresponding carboxylic acid was 58 mol %, which was rare. However, when the neutralization value of this solution was measured, 0.44 mol of carboxyl groups were generated by the reaction. was being generated. Therefore, when 60% hydrogen peroxide solution 509 and 0.9 g of catalyst were added and the reaction was continued for 10 hours,
Tricarboxylcyclopentyl acetic acid was obtained at a production rate of 60 mol% (based on gas chromatography internal standard method). At this time, the amount of carboxyl groups produced calculated from the neutralization value was 0.73 mol%.
実施例7
実施例1の反応器に工業用オレイン酸(ヨウ素価90.
2>28g、水50g、12−タングストリン酸29水
和物2.09を仕込み、90’Cで激しく撹拌しながら
、60%過酸化水素水579を5時間で滴下した1麦、
5時間反応を行なった。Example 7 In the reactor of Example 1, industrial oleic acid (iodine number 90.
2> 1 barley prepared with 28 g, water 50 g, and 2.09 g of 12-tungstophosphoric acid 29 hydrate, and 579 g of 60% hydrogen peroxide solution was added dropwise over 5 hours while stirring vigorously at 90'C.
The reaction was carried out for 5 hours.
反応溶液より水をトッピングした後、減圧上蒸留して、
モノカルボン酸とジカルボン酸を1坪だ。各々の留分の
型組及びガスクロマトグラフィーから対応するカルボン
酸の、工業用オレイン酸に含有される不飽和脂肪酸に対
する生成率を算出した結果、ペラルゴン酸64モル%、
炭素数8以下の短鎖モノカルボン酸27モル%、アゼラ
イン酸79モル%、炭素数10以上の長鎖ジカルボン酸
11モル%、炭素数8以下の短鎖ジカルボン酸5モル%
であった。After topping the reaction solution with water, it was distilled under reduced pressure.
1 tsubo of monocarboxylic acid and dicarboxylic acid. As a result of calculating the production rate of the corresponding carboxylic acid to the unsaturated fatty acid contained in industrial oleic acid from the type of each fraction and gas chromatography, it was found that pelargonic acid was 64 mol%,
27 mol% of short chain monocarboxylic acids with 8 or less carbon atoms, 79 mol% of azelaic acid, 11 mol% of long chain dicarboxylic acids with 10 or more carbon atoms, 5 mol% of short chain dicarboxylic acids with 8 or less carbon atoms.
Met.
[発明の効果]
本発明に係る製造法は、過酸化水素を用いるので、有害
金属を使用することなく安全、かつ安価にカルボン酸を
製造することができる。しかも得られるカルボン酸の収
率は高く、又、生成カルボン酸の分離も比較的容易で高
MA度の目的物を得ることができる。[Effects of the Invention] Since the production method according to the present invention uses hydrogen peroxide, carboxylic acid can be produced safely and inexpensively without using harmful metals. Furthermore, the yield of the obtained carboxylic acid is high, and the separation of the produced carboxylic acid is relatively easy, making it possible to obtain the target product with a high degree of MA.
よって、本発明に係る製造法は工業的に極めて優れたカ
ルボン酸の製造法である。Therefore, the production method according to the present invention is an industrially excellent method for producing carboxylic acids.
Claims (1)
り、タングステン酸、モリブデン酸及びそれらのヘテロ
ポリ酸からなる群から選ばれる1種又は2種以上の触媒
の存在下、過酸化水素により酸化開裂することを特徴と
するカルボン酸の製造法。In producing carboxylic acids by oxidative cleavage of olefins, oxidative cleavage is performed with hydrogen peroxide in the presence of one or more catalysts selected from the group consisting of tungstic acid, molybdic acid, and their heteropolyacids. A method for producing carboxylic acid characterized by the following.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61240129A JPH0761972B2 (en) | 1986-10-08 | 1986-10-08 | Method for producing carboxylic acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61240129A JPH0761972B2 (en) | 1986-10-08 | 1986-10-08 | Method for producing carboxylic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6393746A true JPS6393746A (en) | 1988-04-25 |
JPH0761972B2 JPH0761972B2 (en) | 1995-07-05 |
Family
ID=17054928
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61240129A Expired - Fee Related JPH0761972B2 (en) | 1986-10-08 | 1986-10-08 | Method for producing carboxylic acid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0761972B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5336793A (en) * | 1991-12-11 | 1994-08-09 | Novamont S.P.A. | Preparing carboxylic acids or esters by oxidative cleavage of unsaturated fatty acids or esters |
US5596111A (en) * | 1995-06-05 | 1997-01-21 | North Dakota State University | Method for preparation of carboxylic acids |
JP2001278842A (en) * | 2000-01-28 | 2001-10-10 | Sumitomo Chem Co Ltd | Method for producing esters of 3,3-dimethyl-2- formylcyclopropanecarboxylic acid |
CN1087012C (en) * | 1999-09-29 | 2002-07-03 | 中国科学院兰州化学物理研究所 | Clean catalytic oxidization process for synthesizing adipic acid |
JP2002201174A (en) * | 2000-08-11 | 2002-07-16 | Sumitomo Chem Co Ltd | METHOD FOR PRODUCING beta-HYDROXYHYDROPEROXIDE, KETONE AND CARBOXYLIC ACID AND CATALYST THEREFOR |
JP2008156298A (en) * | 2006-12-25 | 2008-07-10 | Toyota Motor Corp | Method for producing carboxylic acid |
DE102010000459A1 (en) | 2009-02-18 | 2010-09-16 | Toyota Jidosha Kabushiki Kaisha, Toyota-shi | Process for producing carboxylic acid |
-
1986
- 1986-10-08 JP JP61240129A patent/JPH0761972B2/en not_active Expired - Fee Related
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5336793A (en) * | 1991-12-11 | 1994-08-09 | Novamont S.P.A. | Preparing carboxylic acids or esters by oxidative cleavage of unsaturated fatty acids or esters |
US5596111A (en) * | 1995-06-05 | 1997-01-21 | North Dakota State University | Method for preparation of carboxylic acids |
US5939572A (en) * | 1995-06-05 | 1999-08-17 | North Dakota State University Research Foundation | Method for preparation of carboxylic acids |
CN1087012C (en) * | 1999-09-29 | 2002-07-03 | 中国科学院兰州化学物理研究所 | Clean catalytic oxidization process for synthesizing adipic acid |
JP2001278842A (en) * | 2000-01-28 | 2001-10-10 | Sumitomo Chem Co Ltd | Method for producing esters of 3,3-dimethyl-2- formylcyclopropanecarboxylic acid |
JP2002201174A (en) * | 2000-08-11 | 2002-07-16 | Sumitomo Chem Co Ltd | METHOD FOR PRODUCING beta-HYDROXYHYDROPEROXIDE, KETONE AND CARBOXYLIC ACID AND CATALYST THEREFOR |
JP2012092142A (en) * | 2000-08-11 | 2012-05-17 | Sumitomo Chemical Co Ltd | Method for producing ketone and carboxylic acid |
JP2008156298A (en) * | 2006-12-25 | 2008-07-10 | Toyota Motor Corp | Method for producing carboxylic acid |
DE102010000459A1 (en) | 2009-02-18 | 2010-09-16 | Toyota Jidosha Kabushiki Kaisha, Toyota-shi | Process for producing carboxylic acid |
US8309762B2 (en) | 2009-02-18 | 2012-11-13 | Toyota Jidosha Kabushiki Kaisha | Method for producing carboxylic acid |
Also Published As
Publication number | Publication date |
---|---|
JPH0761972B2 (en) | 1995-07-05 |
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